AU2018364032A1 - Zinc-iodine flow battery - Google Patents

Zinc-iodine flow battery Download PDF

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AU2018364032A1
AU2018364032A1 AU2018364032A AU2018364032A AU2018364032A1 AU 2018364032 A1 AU2018364032 A1 AU 2018364032A1 AU 2018364032 A AU2018364032 A AU 2018364032A AU 2018364032 A AU2018364032 A AU 2018364032A AU 2018364032 A1 AU2018364032 A1 AU 2018364032A1
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positive
negative
electrolyte
zinc
iodine
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Xianfeng Li
Congxin XIE
Huamin Zhang
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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Priority claimed from CN201711091359.4A external-priority patent/CN109755604B/en
Priority claimed from CN201711090856.2A external-priority patent/CN109755620B/en
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Abstract

The present invention relates to a zinc-iodine flow battery, which is a zinc-iodine single flow battery or a zinc-iodine dual flow battery and comprises a pile composed of one single battery or two or more single battery circuits connected in series. The single battery comprises a positive electrode terminal plate, a positive and a negative electrode current collector, a positive electrode having a flow frame, a membrane, a negative electrode having a flow frame, and a negative electrode terminal plate which are sequentially laminated. In the electrolyte solution in a negative electrode electrolyte solution storage tank, the electrolyte circulates between a negative electrode cavity and the storage tank by means of a pump, and a branch pipeline for the positive electrode electrolyte circulation is provided on a negative electrode pipeline. The positive electrolyte solution and the negative electrolyte solution of the dual flow battery are the same, both being a mixed aqueous solution of an iodine salt and a zinc salt, and the membrane is a porous membrane free of an ion exchange group. Furthermore, the positive and negative electrolyte solutions are both neutral, overcoming the corrosiveness problem of strong acid and strong alkaline electrolytes of the conventional flow batteries, and meanwhile, the battery has high current density, long cycle life and low cost.

Description

Zinc Iodine Flow Battery
Technical field [001] The invention relates to the field of flow battery, in particular to the field of zinc iodine flow battery.
Background technology [002] The massive consumption of fossil energy has caused energy crisis and environmental problems. The development and utilization of renewable energy has received great attention all over the world. However, the discontinuity and instability of renewable energy, such as wind and solar energy, enable the difficult utilization of it, therefore, the realization of the continuous supply of renewable energy via the large scale energy storage technology is the key to solve the above problem. Due to the advantages of flexible design (energy and power are designed separately), high safety, long cycling life and not limited by terrain, flow battery has become one of the best technologies for large-scale energy storage. Among them, all vanadium flow battery has entered the commercial demonstration stage with its unique technical advantages.
[003]At present, the relatively mature flow system technologies include all vanadium flow batteries, zinc bromine flow batteries, sodium polysulfide bromine and other systems. However, as for vanadium flow battery, the high cost, acidity and corrosiveness of electrolyte and the strongly oxidizing sulfuric acid and VO2 enable high requirement for the membrane; zinc bromine and sodium polysulfide bromine flow battery would generate corrosive bromine during the charging process. At the same time, the high vapor pressure, severe volatilization and environmental pollution of Br2 need to be further considered.
Zinc iodine flow batteries employ neutral zinc and iodide salt as electrolyte, which has the advantage of high solubility and energy density. Compared with Cl2 and Br2, iodine is less corrosive. In the meantime, iodine exists in the form of I3' and the vapor pressure is much lower, which makes the zinc-iodine flow battery a promising system. Same as common flow batteries, the zinc iodine flow battery (replaced as zinc iodine dual-flow battery in PCT) adopts a dual-pump and pipeline design. During the charge and discharge process, the positive and negative electrolytes circulate between the battery cavity and electrolyte storage tank. However, because batteries require electrolyte circulation systems such as pumps and storage tanks, the energy efficiency of the system is reduced. On the other hand, the battery auxiliary equipment such as pumps and storage tanks complicate the battery system and reduce the energy density of the system. Therefore, research on single flow battery based on dual-flow system and reducing the energy loss of the system is an important way to improve the energy utilization efficiency and energy density of the whole system. In addition, currently reported zinc iodine dual-flow batteries usually use expensive Nation membranes, but the above-mentioned ion-exchange membranes could be easily contaminated in the zinc-iodine system, leading to an increase in ohmic resistance and poor cycle stability of the battery. In addition, zinc iodine flow batteries use Znl2 as the electrolyte, which is easily oxidized by air to generate ZnO precipitation. At the same time, I2 would be desposited on the positive electrode which restricted the stability of the electrolyte and then the cycling life. Therefore, the reported working current density is less than 10 mA/cm2, which lead to a low power density.
Summary of the invention [004] To solve the above problems, the content of the invention is as follows:
[005] A zinc iodine flow battery comprises either a single battery or a stack. The single flow battery includes a porous electrode and cavity on the positive side which is filled with electrolyte. In a zinc iodine dual-flow battery, the positive or negative electrolyte circulates inside the battery and in the storage tank through a pump and a pipeline, for single flow battery, there is no pump or pipeline on the positive side, and the electrolyte is stored in the porous electrode and cavity. As for the negative side, the electrolyte in the battery and in the negative storage tank could be circuited through the pump and pipeline, and pipeline is provided with a branch for the circulation of the positive electrolyte. The dual-flow battery also includes positive and negative electrolyte storage tanks, which contain the positive and negative electrolyte, respectively.
[006] When the battery is being charged, Γ is oxidized to I3‘ or I2 on the positive electrode, and Zn2+ on the negative electrode is reduced to Zn; during discharging, the positive electrolyte is reduced to Γ, and the Zn is oxidized to Zn2. The membrane between the positive and negative electrodes prevents I3' from migrating to the negative electrode while conducting the supporting electrolyte.
[007] Compared with the dual-flow battery, the zinc iodine single flow battery eliminates the positive storage tank and pump on the positive side, the positive electrolyte is sealed in the positive porous electrode. Furthermore, the negative pipe is provided with a branch pipe for positive electrolyte circulation. The structure of single flow battery includes positive and negative end plates, membrane, positive electrode, negative electrode, current collector, flow frame, pump and pipeline. The structure of the dual-flow battery includes positive end plate, negative end plate, membrane, positive electrode, negative electrode, current collector, flow frame, pump and pipeline.
[008] The positive electrolyte composition includes iodine salt, zinc salt, and the supporting electrolyte. Iodine salt is one or more of Cal2, Mgl2, KI and Nal, with a concentration of 2~8 mol/L. The active substance in the negative electrolyte is one or more of Zn(NO3)2, ZnBr2, ZnSO4> ZnCl2, with the concentration of 1~4 mol/L, the molar ratio of iodine and zinc in the electrolyte of dual-flow battery is 2:1, the supporting electrolyte of single flow battery is one or more of KC1, KBr, NaCl and the concentration is l~2mol/ L. Among them, KI is a preferred iodine salt, ZnBr2 is a preferred zinc salt, KC1 is a preferred supporting electrolyte and the concentration is 1 mol/L for the dual-flow battery.
[009] The electrode material is one of carbon felt, graphite plate, metal plate or carbon cloth. The electrode material is preferably carbon felt.
[010] As for the zinc iodine flow battery, the membrane used for the zinc iodine single flow battery is a porous membrane without ion exchange groups or a composite membrane. The membrane used for a duel-flow battery is a porous membrane without ion exchange groups or a composite membrane.. The substrate is a porous membrane, which includes one or more of polyethersulfone (PES), polyethylene (PE), polypropylene (PP), polysulfone (PS), polyetherimide (PEI), and polyvinylidene fluoride (PVDF). The membrane thickness is 100-1000 pm, preferably 500-1000 pm. The pore diameter is about 10-100 nm with the porosity of 30%~70%. Polyethylene (PE) and polypropylene (PP) are preferred porous substrate. In addition, as for zinc iodine single flow battery, the porous membrane is coated with a dense polymer layer to improve the coulomb efficiency of the battery; the material of which include: polybenzimidazole (PBI), Nation resin and (polytetrafluoroethylene) PTFE. Nation resin is preferred and the thickness of the coating is 1-10 pm.
[Oil] The invention has the following beneficial effects:
1. Compared with the dual-flow battery, the structure of zinc iodine single flow battery is greatly simplified, which improves the energy density of the battery. At the same time, the energy loss of the system is reduced, which improves the energy efficiency of the system. In addition, the concentration of electrolyte is very high, which is suitable for single flow battery design; same as dual-flow battery, zinc iodide single flow battery solves the strong acid and alkali issue of electrolyte and the cost of electrolyte is relatively low; at the same time, high current density and the power density of battery could also be achieved.
2. The positive and negative electrolytes are the same, which effectively alleviates the crossover issue due to the similar osmotic pressure of the positive and negative electrolytes. Therefore, the coulomb efficiency could be greatly improved, which effectively reduces the system maintenance costs caused by electrolyte migration. Furthermore, the electrolyte could be recovered online, which greatly saves the replacement cost of the electrolyte and demonstrates a good application prospect.
3. Iodine and zinc salt could be employed as the reactant of dual-flow battery with low cost and environment friendliness; the high solubility of zinc and iodine salt achieved high energy density. Furthermore, the high electrochemical activity of electrolyte enables a high current density and power density of the battery; at the same time, the negligible corrosiveness of electrolyte could greatly reduce the environmental burden. The invented zinc iodine flow battery solves the issue of strong acid and alkali of electrolyte, besides, the supporting electrolyte could improve the conductivity of the electrolyte and then the voltage efficiency.
4. The low-cost porous membrane replaces the traditional Nation 115 membrane, which greatly reduces the cost of the stack. In addition, the porous structure of the membrane could improve the conduction of neutral ions and the current density of the battery can reach 140 mA/cm2, which means great improvement in the voltage efficiency. Most importantly, the porous structure of the porous membrane is filled with oxidized I3‘, which can alleviate the short-circuit issue that caused by zinc dendrite after overcharging, so the battery could be self-recovered and greatly improve the stability of the battery. In addition, Nation coating can effectively alleviate I2/I3 crossover and significantly improve the coulomb efficiency of single flow battery (higher than 98%).
5. The traditional zinc iodine flow battery employes Znl2 as the reactant, which tends to be oxidized into ZnO at room temperature and reduces the cycle stability of the battery; replacing Znl2 with KI greatly improves the stability of the positive electrolyte and the price of KI is much lower than that of Znl2, so the cost of the electrolyte could be greatly reduced.
6. The introduction of Br' by ZnBr2 could complex with I2 to form I2Br‘ that inhibit the precipitation of I2 when the battery operates at high SOC and high current density, which greatly improves the cycling stability of the battery.
Brief description of drawings [012] Figure 1 is the structural diagram of the zinc iodine single flow battery of the invention. Among them, 1 refers to positive and negative bipolar plates; 2 refers to positive and negative current collectors; 3 refers to positive and negative flow frames; 4 is the membrane; 5 refers to positive electrolyte inlet and outlet valves; 6 is the electrolyte storage tank; 7 is pump.
Figure 2 shows the single battery cycle performance of the zinc iodine single flow battery according to example 1; the positive and negative electrolytes are ZnBr2:4 M, KI: 8 M, KC1: IM, and the porous membrane with the thickness of 900 pm.
Figure 3 shows the energy density of the zinc iodine single flow battery according to example 1; the positive and negative electrolyte is ZnBr2:4 M, KI: 8 M, KC1: 1 M, and the porous membrane with the thickness of 900 pm.
Figure 4 shows the cycle performance of the zinc iodine single flow battery according to example 3; the positive and negative electrolyte is ZnBr2:4 M, KI: 8 M, KC1: 1 M, and the porous membrane thickness: 500 pm.
Figure 5 shows the cycle performance of the zinc iodine single flow battery according to example 5; the positive and negative electrolyte is ZnCl2:4 M, KI: 8 M, KC1: 1 M, and the porous membrane thickness: 900 pm.
Figure 6 shows the cycle performance of the zinc iodine single flow battery according to Example 7; the positive and negative electrolyte is ZnBr2:4 M, Nal: 8 M, KC1: 1 M, and the porous membrane thickness: 900 pm.
Figure 7 shows the energy density diagram of the zinc iodine single flow battery according to Example 7; the positive and negative electrolyte is ZnBr2:4 M, Nal: 8 M, KC1: 1 M, and the porous membrane thickness: 900 pm.
Figure 8 shows the cycle performance of the zinc iodine single flow battery according to comparative example 2; the positive and negative electrolyte is Znl2:4 M, porous membrane thickness : 900 pm.
Figure 9 shows the cycle performance of the zinc iodine single flow battery according to comparative example 3; the positive and negative electrolytes are ZnBr2:4 M, Nal: 8 M, KC1: 1 M, Nation 115 film thickness: 125μιη.
Figure 10 shows the cycle performance of the zinc iodine single flow battery according to comparative example 5; the positive and negative electrolyte is ZnBr2:4 M, Nal: 8 M, KC1: 1 M, and the porous film thickness is 65 μιη.
Figure 11 is the structural diagram of zinc iodine dual-flow battery using porous membrane: 1 refers to the positive and negative pumps; 2 refers to the positive and negative electrolyte storage tank; 3 refers to the positive and negative end plates; 4 refers to the positive and negative current collectors; 5 refers to the positive and negative flow frames; 6 is the membrane.
Figure 12 shows the single battery cycle performance diagram of the zinc iodine dual-flow battery according to example 1; the positive and negative electrolyte is ZnBr2:2.5 M, KI: 5 M, KC1: 1 M, and the porous membrane thickness is 900 μιη.
Figure 13 shows the single battery cycle performance diagram of the zinc iodine dual-flow battery according to example 2; the positive and negative electrolyte is ZnBr2:3 M, KI: 6 M, KC1: IM, the porous membrane thickness is 900 μιη.
Figure 14 shows the energy density diagram of the single cell of the zinc iodine dual-flow battery according to example 1; the positive and negative electrolyte is ZnBr2:2.5 M, KI: 5 M, KC1: 1 M: Im, the porous membrane thickness is 900 μιη.
Figure 15 shows the energy density diagram of the single cell of the zinc iodine dual-flow battery according to example 2; the positive and negative electrolyte is ZnBr2:3 M, KI: 6 M, KC1: IM, the porous membrane thickness is 900 μιη.
Figure 16 shows the single battery cycle performance diagram of the zinc iodine dual-flow battery according to example 3; the positive and negative electrolyte is ZnBr2:2m, KI: 4 M, KC1: 1 M, the porous membrane thickness is 900 μιη.
Figure 17 shows the single cell cycle performance diagram of the zinc iodine dual-flow battery according to example 4; the positive and negative electrolyte is ZnBr2:l M, KI: 2 M, KC1: 1 M , the porous membrane thickness is 900 μιη.
Figure 18 shows the single battery cycle performance diagram of the zinc iodine dual-flow battery according to example 6; the positive and negative electrolyte is ZnBr2:3 M, KI: 6 M, KC1: 1 M, and the thickness of the porous membrane is 500 μιη.
Figure 19 shows the single battery cycle performance of the zinc iodine dual-flow battery according to example 12; the positive and negative electrolyte is ZnSCfoS M, KI: 6 M, KC1: 1 M, and the thickness of the porous membrane is 900 μιη.
Figure 20 single battery cycle performance diagram of zinc iodine dual-flow battery according to example 14; positive and negative electrolyte is ZnBr2:3 M, KI: 6 M, and the thickness of porous membrane is 900 pm.
Figure 21 demonstrates the ratio performance diagram of zinc iodine dual-flow battery according to example 4; the structure of the single cell battery includes successively: positive end plate, positive current collector, positive flow frame, membrane, negative flow frame and negative end plate. The composition of electrolyte in the battery is 2 M KI, 1 M ZnBr2, and 2 M KC1, flow rate is 10 ml/min, charging current density is 60-140 mA/cm2, the battery is terminated by the capacity and voltage double cut-off: the charging cut-off time is 45 minutes and the voltage is 1.5 V, discharging cut-off voltage is 0.1 V.
Figure 22 is a temperature dependent performance diagram of the zinc iodine dual-flow battery assembled in example 4. Battery temperature dependent performance test: the structure of the single battery is as follows: positive end plate, positive current collector, positive flow frame, membrane, negative flow frame and negative end plate. The composition of electrolyte in the battery is 2 M KI, 1 M ZnBr2, and 2 M KC1, flow rate is 10 ml/min, charging current density is 80 mA/cm2, the battery is terminated by the capacity and voltage double cut-off: the charging cut-off time is 45 minutes and the voltage is 1.5 V, discharging cut-off voltage is 0.1 V, temperature range is 10°C~65°C.
Figure 23 demonstrates the voltage curve of a single zinc-iodine dual-flow battery according to example 2. The structure of the single battery is as follows: positive end plate, positive current collector, positive flow frame, membrane, negative flow frame and negative end plate. The composition of electrolyte in the battery is 6 M KI, 3 M ZnBr2, and 1 M KC1 flow rate is 10 ml/min, charging current is 80 mA/cm2, the battery is terminated by the capacity and voltage double cut-off: the charging cut-off time is 45 minutes and the voltage is 1.5 V, discharging cut-off voltage is 0.1 V. Charge for 1 hour until the battery is short circuited, then reduce the charging time to 45 mins to continue the battery cycling.
Figure 24 demonstrates a voltage curve diagram of a zinc-iodine dual-flow battery stack according to example 2. The structure of the stack is: a positive electrode end plate, a current collector, nine batteries each comprises a positive electrode with flow frame, a membrane, a negative electrode with a flow frame, and finally a current collector and a negative electrode end plate connected in series. The electrolyte composition of the battery is 6 M KI, 3 M ZnBr2, and 1 M KC1 with a flow rate of 10 mL/min. The charging current density was 80 mA/cm2 and the charge cut-off voltage is 13 V with a discharge cut-off voltage of 1 V. Charge for 1 h until the battery is short-circuited, then reduce the charging time to 45 mins to continuously evaluated the battery.
Figure 25 is the cyclic performance diagram of the zinc iodine dual-flow battery stack according to example 2; the stack assembled with nine single battery connected in series.
Figure 26 shows the cycle performance of a single cell zinc iodine dual-flow battery according to comparative example 1; the positive and negative electrolyte are ZnBr2:2.5 M, KI: 5 M, KC1: 1 M Nation 115 membrane with the thickness of 125 pm.
Figure 27 shows the cycle performance of a single zinc iodine dual-flow battery according to comparative example 4; the positive and negative electrolyte is Znl2:3 M, and the thickness of the porous membrane is 900 pm.
Figure 28 shows the cycle performance of a single zinc iodine dual-flow battery according to comparative example 5; the positive and negative electrolyte is Znl2:3 M, KI: 5 M, KC1: IM, porous membrane with the thickness of 65 pm
Figure 29 is the cycle performance diagram of a single cell zinc iodine single flow battery according to preferred example 1; the positive and negative electrolyte is ZnBr2:4 Μ, KI: 8M, KC1: 1 M, the composite membrane is PE porous membrane substrate with 7 pm Nation resin coating.
Figure 30 is the energy density diagram of zinc iodine single flow battery according to preferred example 1; the positive and negative electrolyte is ZnBr2:4 M, KI: 8 M, KC1: 1 M, the composite membrane is PE porous substrate with 7 pm Nation resin coating.
Figure 31 shows the cycle performance diagram of the zinc iodine single flow battery according to preferred example 2; the positive and negative electrolyte is ZnBr2:4 M, KI: 8 M, KC1: 1 M, the composite membrane is PE porous substrate with 7 pm Nation resin coating.
Embodiments
The evaluation of zinc iodine dual-flow battery and single flow battery: the structure of the single battery include, sequentially, positive electrode plate, current collector, carbon felt positive electrode with flow frame, membrane, carbon felt negative electrode with a flow frame, and negative end plate. The flow rate of the electrolyte in the battery was 10 mL/min, the charging current density was 80 mA/cm2, the battery was terminated by the capacity and voltage double cut-off: the charging time was 45 minutes and the voltage was 1.5 V, discharging cut-off voltage was 0.1 V.
Examples Electrolyte Composition (mol/L) membrane Thickness (pm) CE VE EE
1 8MKI, 4MZnBr2, 1MKC1 PE 900 96% 80% 77%
2 6MKI, 3MZnBr2, 1MKC1 PE 900 96% 81% 78%
3 8MKI, 4MZnBr2, 1 M KC1 PE 500 91% 80% 73%
4 6MKI, 3MZnBr2, 1 M KC1 PE 500 91% 81% 74%
5 8MKI, 4MZnCl2, 1 M KC1 PE 900 92% 71% 65%
6 6MKI, 3MZnCl2, 1 M KC1 PE 900 93% 70% 65%
7 8MNaI, 4MZnBr2, 1 M KC1 PE 900 88% 78% 68%
8 6MNaI, 3MZnBr2, 1 M KC1 PE 900 90% 78% 70%
9 8MKI, 4MZnBr2 PE 900 96% 78% 75%
10 6MKI, 3MZnBr2 PE 900 97% 78% 76%
Preferred example 1 8MKI, 4MZnBr2, 1 M KC1 Composite membrane 900 97% (85%) (82%)
Preferred example 2 8MKI, 4MZnBr2, 1 M KC1 Composite membrane 500 96% (86%) (81%)
Comparativ e example Electrolyte Composition (mol/L) membrane Thickness (gm) CE VE EE
1 Znl2 3 M PE 900 90% 81% 73%
2 Znl24 M PE 900 89% 78% 69%
3 8MKI, 4MZnBr2, 1 M KC1 Nafion 115 125 99% 70% 69%
4 6MKI, 3MZnBr2, 1 M KC1 Nafion 212 50 99% 68% 67%
5 KI 5 M, ZnBr2 2.5 M, 1 M KC1 PE 65 74% 88% 65%
Figures 2 to 3 are graphs of cycle performance and energy density of the battery under the most preferred conditions. With KI/ZnBu as the electrolyte, the battery assembled with porous membrane achieved excellent cycle stability. Meanwhile, the application of porous membrane greatly improved the ion conductivity, the working current density of the battery can reach 80 mA/cm2 with the high power density. At the same time, the concentration of KI in the electrolyte can reach about 8 M and the energy density is greater than 90 Wh/L.
Compared with the most preferred example, the battery in Figure 4 employs a much thinner porous membrane (500 pm), and the coulombic efficiency of the battery decreases due to the increase of electrolyte crossover. The electrolyte in Figure 5 employed ZnCh rather than ZnBr2, the performance is greatly reduced and the stability is deteriorated. This is due to the instability of the electrolyte; during charging, the desposition formed in the positive elelctode and ZnCh in the negative electrolyte would hydrolyze and precipitate. In Figure 6, when Nal was substituted with KI, the battery efficiency decreased. In particular, the voltage efficiency drop is mainly caused by the decrease of the electrolyte conductivity , which further decreased the energy density of the battery in Figure 7.
Figures 8-10 are comparative experiments. Figure 8 employed Zrffi as the electrolyte of the battery. The decrease of efficiency was mainly due to the low ion conductivity of the Znl2 solution. Further, the battery performance is unstable due to the precipitation of electrolyte. Figure 9 employed Nation 115 membrane for the battery assembly. During the charge and discharge process, serious membrane fouling occurred on the membrane surface, which intensified the battery polarization and decreased the battery performance. Figure 10 used a much thinner porous membrane, the cross-contamination of electrolyte was greatly intensified, and the efficiency of the battery, especially the coulomb efficiency, was severely reduced.
A preferred example employed a Nafion-coated composite membrane as the membrane. Figure 29 shows the performance of a battery that used composite membrane with the thickness of 900 pm. The electrolyte was a mixed solution of KI and ZnBr2. Due to the Donnan exclusion of Nation coating, the columbic efficiency of the battery was greatly improved. In addition, the battery used a thinner composite membrane (500 pm), and the coulombic efficiency of the battery slightly decreased.
The evaluation of zinc-iodine dual-flow battery and single flow battery: the structure of a single battery contains, sequentially: a positive electrode plate, a current collector, a carbon felt positive electrode with a flow frame, a membrane, and a battery with a flow frame, a carbon felt negative electrode with a flow frame, and a negative end plate. The flow rate of the electrolyte in the battery was 10 mL/min, the battery was terminated by the capacity and voltage double cut-off: the charging cut-off time was 45 minutes and the voltage was 1.5 V, discharging cut-off voltage was 0.1 V
Examples Electrolyte (mol/L) membrane Thickness (pm) CE VE EE
1 KI5M, ZnBr2 2.5 M, 1 M KC1 PE 900 94% 85% 80%
2 KI6 M, ZnBr2 3 M, 1 M KC1 PE 900 94% 85% 80%
3 KI 4 M, ZnBr2 2 Μ, 2 M KC1 PE 900 94% 85% 80%
4 KI 2 Μ, ZnBr2 1 Μ, 2 M KC1 PE 900 94% 86% 81%
5 KI 5 Μ, ZnBr2 2.5 Μ, 1 M KC1 PE 500 87% 86% 75%
6 KI 6 Μ, ZnBr2 3 Μ, 1 M KC1 PE 500 86% 86% 74%
7 Nal 5 Μ, ZnBr2 2.5 Μ, 1 M KC1 PE 900 94% 83% 78%
8 Nal 6 Μ, ZnBr2 3 Μ, 1 M KC1 PE 900 94% 82% 77%
9 KI 5 M, ZnCl2 2.5 Μ, 1 M KC1 PE 900 91% 82% 75%
10 KI 6 Μ, ZnCl2 3 Μ, 1 M KC1 PE 900 90% 81% 72%
11 KI 5 M, ZnSO4 2.5 Μ, 1 M KC1 PE 900 76% 81% 61%
12 KI 6 M, ZnSO4 3 Μ, 1 M KC1 PE 900 75% 80% 60%
13 KI 5 Μ, ZnBr2 2.5 Μ PE 900 95% 83% 79%
14 KI 6 M, ZnBr2 3 Μ PE 900 95% 83% 79%
Comparative example Electrolyte (mol/L) membrane Thickness (pm) CE VE EE
1 KI5M, ZnBr2 2.5 M, 1 M KC1 Nafion 115 125 99% 81% 80%
2 KI5M, ZnBr2 2.5 M, 1 M KC1 Nation 212 50 98% 83% 81%
3 Znl2 2.5 M PE 900 99% 71% 70%
4 Znl2 3M PE 900 98% 70% 68%
5 KI 5 M, ZnBr2 2.5 M, 1 M KC1 PE 65 74% 88% 65%
Figure 11-17 show zinc iodine dual-flow batteries that employed ZnBr2 and KI as the active substance, KC1 as the supporting electrolyte with a 900 gm porous membrane. The battery can continuously run stably for more than 1000 cycles at 80 mA/cm2. Above all, the energy efficiency is greater than 80% with the energy density above 80 Wh/L. The advantages of the above system include: the introduction of Br'in ZnBr2 can form a complex agent of I2Br‘, thereby inhibiting the precipitation of I2; the replacement of traditional Znl2 with KI can avoid the formation of zinc oxide and hydroxide during the charge and discharge process. The employment of porous membranes benefit the conduction of neutral ions, which improves the operating current density and power density of the battery. In addition, the absence of ion exchange groups in the membrane can greatly reduce the membrane fouling issue and improve the cycle stability of the battery.
Compared with the most preferred example: Figure 18 employs a thinner porous membrane which resulted in a drop of performance especially the coulomb efficiency. This is mainly due to the employment of a thinner membrane that lead to much more serious cross-contamination. In Figure 19, ZnSCC replaced ZnBr2 and the voltage efficiency of the battery was greatly reduced, which indicates that the sulfate ion affected the electrochemical kinetic of electrolyte; in Figure 20, when the supporting electrolyte was removed, the voltage efficiency of the battery was reduced slightly.
Figures 21 to 25 demonstrate that, under preferred conditions, the battery displayed excellent rate performance and temperature dependent performance; in addition, the porous membrane could eliminate the zinc dendrites formed on the negative electrode as the pore structure was filled with oxidized I3‘, which could react with the zinc dendrite. Therefore, the single battery and the battery stack can self-recovered after a micro short circuit occur, which greatly improves the stability of the battery. Most importantly, the battery stack can continuously run stably for more than 300 cycles at 80 mA/cm2.
Compared with the preferred example: Nation 115 membrane was used for the battery in Figure 26. Due to the poor conductivity of the membrane, the voltage efficiency of the battery was lower than that of optimal example, however, the employment of Nation 115 membrane greatly reduced the crossover issue and greatly improved the coulombic efficiency of the battery. However, the performance of the battery deteriorated sharply after 15 cycles, which was due to the serious membrane fouling of the Nafionll5 membrane caused by I2 and Zn dendrite, the membrane resistance increased greatly and the polarization was intensified. Figure 27 used Znl2 as the electrolyte and the battery performance was severely degraded, which was caused by the instability of the positive and negative electrolytes. The positive electrolyte would form I2 precipitation during the charging process and the negative electrolyte would form zinc oxide and hydroxide. Figure 28 used a much thinner porous membrane, the cross-contamination of the electrolyte was intensified and the coulombic efficiency of the battery was greatly reduced.

Claims (8)

  1. We claim:
    1. The zinc iodine flow battery, which related a zinc iodine single flow battery or a zinc iodine dual-flow battery; The single flow battery comprises a negative electrolyte storage tank, a zinc iodine single flow battery includes a single battery or a cell stack that assembled with more than two single battery circuits in series; The single battery comprises a positive end plate, a positive current collector, a positive electrode with a flow frame, a membrane, a negative electrode with a flow frame, a negative current collector and a negative end plate; the electrolyte in the negative electrolyte storage tank could be circuited between the negative cavity (the cavity between the membrane and the negative current collector is called the negative cavity; the negative cavity is provided with a negative inlet and a negative outlet) and the electrolyte storage tank by pump; the negative electrolyte storage tank is connected with the negative inlet and outlet through the negative inlet and outlet of pipeline respectively; at the same time, the negative inlet and outlet of pipe are respectively provided with a branch for the circulation of the positive electrolyte; (the cavity between the membrane and the positive current collector is called a positive cavity; the positive cavity is provided with a positive inlet and a positive outlet); the branch on the negative inlet of pipeline is connected with the positive inlet on the positive cavity, and the branch on the negative outlet of pipeline is connected with the positive outlet on the positive cavity;
    The dual-flow battery comprises a single battery or a stack that assembled with more than two single battery circuits in series; the single battery comprises a positive end plate, a current collector, a positive electrode with a flow frame, a membrane, a negative electrode with a flow frame, a current collector, and a negative end plate; the positive electrolyte in the positive electrolyte storage tank flows through the positive electrode by the pipeline and pump; the negative electrolyte in the negative electrolyte tank could flows through the negative electrode by the pipeline and pump; the positive electrolyte and the negative electrolyte are the same, which are the mixture aqueous solutions of iodine and zinc salt; the membrane is a porous membrane without ion exchange groups or composite membrane.
  2. 2. The zinc-iodine flow battery according to claim 1, wherein the membranes of the single-flow battery and the dual-flow battery are both porous membranes without ion exchange groups or composite membranes.
  3. 3. The zinc-iodine flow battery according to claim 1, wherein the iodine salt is one or more of Cai2, Mgl2, KI, and Nal, and the molar concentration of the iodized salt in the electrolyte is 2 to 8 mol/L; the zinc salt is one or more of ZnNO4, ZnBr2, ZnSO4, and ZnCl2, and the molar concentration of the zinc salt in the electrolytic solution is 1 to 4 mol/L; the molar ratio of iodine and zinc in the electrolytic solution is preferably between 2: 1, wherein zinc salt is preferably ZnBr2, and iodine salt is preferably KI.
  4. 4. The zinc-iodine flow battery according to claim 1 or 3, wherein the electrolyte solution contains a supporting electrolyte, and the supporting electrolyte in a single-flow battery is one or more of KC1, KBr, and NaCl; the electrolyte of dual-flow battery is one or more of KC1, K2SO4, KBr; the concentration is 1 to 2 mol/L and the supporting electrolyte is preferably KCL
  5. 5. The zinc-iodine flow battery according to claim 1 or 2, wherein the membrane is a porous membrane without ion-exchange groups, including one or more of polyethersulfone (PES), polyethylene (PE), polypropylene (PP), polysulfone (PS), polyetherimide (PEI), and polyvinylidene fluoride (PVDF); the membrane is a porous membrane, and the thickness of a single-flow battery is 100 to 1000 pm; the thickness of membrane employed for the dual-flow battery is 150-1000pm, preferably 500-1000 pm; the porous membrane material is preferably PE, PP, pore size is 1-10 nm, and porosity is 20%~70%.
  6. 6. The zinc-iodine flow battery according to claim 1 or 2, wherein the composite membrane is a porous membrane without ion-exchange groups coated with a dense polymer layer on the surface and the polymer layer material is one or more of polybenzimidazole (PBI), Nafion resins and polytetrafluoroethylene (PTFE), preferably Nafion resin, and the thickness of the coating is 1-10 pm.
  7. 7. The zinc-iodine flow battery according to claim 1, characterized in that during charging the fin the positive electrolyte undergoes an oxidation reaction to generate one or more of I3‘ and I2, preferably I2; on the negative electrode Zn2+ undergoes a reduction reaction to form Zn; during discharge, the I3‘ or I2 undergoes a reduction reaction to generate Γ on the positive electrode, and the Zn undergoes an oxidation reaction to generate Zn2.
  8. 8. The zinc-iodine flow battery according to claim 1, wherein the electrode material is one of carbon felt, graphite plate, metal plate, or carbon cloth, preferably carbon felt.
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